CN110467540A - A kind of synthetic method of fluorine-containing polyethyleneimine - Google Patents
A kind of synthetic method of fluorine-containing polyethyleneimine Download PDFInfo
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- CN110467540A CN110467540A CN201910861974.1A CN201910861974A CN110467540A CN 110467540 A CN110467540 A CN 110467540A CN 201910861974 A CN201910861974 A CN 201910861974A CN 110467540 A CN110467540 A CN 110467540A
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- Prior art keywords
- fluorine
- polyethyleneimine
- containing polyethyleneimine
- functional material
- synthetic method
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- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 77
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 47
- 239000011737 fluorine Substances 0.000 title claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 42
- -1 perfluoroalkyl carboxylic acid halides Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 238000003682 fluorination reaction Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- 239000012296 anti-solvent Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000011243 crosslinked material Substances 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 238000012637 gene transfection Methods 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 12
- 238000013019 agitation Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 7
- 229920002313 fluoropolymer Polymers 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000001728 nano-filtration Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- GSJWYIDMIRQHMV-UHFFFAOYSA-N butanoyl fluoride Chemical compound CCCC(F)=O GSJWYIDMIRQHMV-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UFFSXJKVKBQEHC-UHFFFAOYSA-N heptafluorobutyric anhydride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OC(=O)C(F)(F)C(F)(F)C(F)(F)F UFFSXJKVKBQEHC-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- AQQBRCXWZZAFOK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O AQQBRCXWZZAFOK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DXAOXPFFQPRUGW-UHFFFAOYSA-N FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)F.Cl Chemical compound FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)F.Cl DXAOXPFFQPRUGW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001409 amidines Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- HMRWGKIZOBXNRB-UHFFFAOYSA-N octane-1-sulfonyl fluoride Chemical compound CCCCCCCCS(F)(=O)=O HMRWGKIZOBXNRB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C311/05—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms to acyclic carbon atoms of hydrocarbon radicals substituted by nitrogen atoms, not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a kind of synthetic methods of fluorine-containing polyethyleneimine.The fluorine-containing polyethyleneimine is prepared by polyethyleneimine and perfluoroalkyl carboxylic acid halides or the condensation of per-fluoroalkyl sulfonyl halogen.Preparation method are as follows: polyethyleneimine is dissolved in solvent, perfluoroalkyl carboxylic acid halides or per-fluoroalkyl sulfonyl halogen are added dropwise into reaction system in a heated condition, removes solvent after being stirred to react, obtains the fluorine-containing polyethyleneimine cross-linked material.The material can be applied to the fields such as the preparation of seperation film, the preparation of adsorbent and gene transfection Materials, have the performances such as solvent resistant, acid and alkali-resistance, antipollution.
Description
Technical field
The invention belongs to macromolecule modified technical fields, and in particular to one kind can make seperation film, adsorbent, gene transfection material
The synthetic method of the fluorine-containing polyethyleneimine of material.
Background technique
Fluorine material has the characteristics such as excellent thermal stability, chemical stability and low-surface-energy, with polytetrafluoroethylene (PTFE), gathers
Vinylidene is that the fluoropolymer of representative has mature application in terms of separating film preparation.Fluoropolymer is in all multi-solvents
In dissolubility it is poor, traditional phase separation method is unable to satisfy the exploitation demand of a greater variety of fluoropolymer seperation films.Closely
Nian Lai has the document and patent report that functional fluoropolymer film is prepared using water-soluble preferable fluorine-containing cross-linked material successively.Middle promulgated by the State Council
Bright patent ZL CN 2 201010589192.6 " film function monomer and its nanofiltration membrane preparation method containing hexafluoroisopropanol group "
A kind of cross-linked material of function monomer containing hexafluoroisopropanol of middle invention with acyl chloride material by interface-cross-linked, it is anti-by controlling
Condition optimizing is answered to go out fluorine-containing nanofiltration membrane, prepared fluorine-containing nanofiltration membrane is preferable to bivalent cation and anion rejection effect, and
And there is very strong resistance to free chlorine oxidation susceptibility.Li Yafei, Jiang Zhongyi et al. pass through the condensation of triethylene tetramine and perfluoro caprylic acid
Reaction prepares the fluorine-containing polyamine in water-soluble, passes through the amido and polyamide film surface carboxylic acid in fluorine-containing polynary amine structure
Condensation in nanofiltration membrane surface modification full-fluorine group, the fluorine-containing nanofiltration membrane show fabulous antifouling property (Y. Li et al,
J. Membr. Sci, 2014,455,15-23.).The fluoropolymer used in foregoing invention suffers from preferable water-soluble
Property, it is suitable for more film-forming methods.
Polyethyleneimine is a kind of Polycationic water soluble polymer, has linear and two kinds of branched knots
Structure, there are a large amount of amidos in skeleton, and wherein primary amine, secondary amine, tertiary amine ratio 1:2:1 in branched polyethylene imine structure, have
Fabulous reactivity.Polyethyleneimine can prepare microballoon such as Chinese patent by being crosslinked other small molecules
ZL201110140086.4, United States Patent (USP) US2010/0267108A1 etc. or thin-film material, in gene transfection Materials, adsorption material
There is more application in material, separation membrane material, active amine can carry out a variety of chemical modifications in structure.Chinese invention patent
One has been invented in ZL CN 201610584829.X " a kind of the PEI compounds of modification and its preparation method and application "
The primary amine hydrogen in polyethyleneimine that the PEI compounds of kind modification are 1.8k to molecular weight by heptafluorobutyric anhydride replaces
It obtains, can be used as excellent genes delivery system.However heptafluorobutyric anhydride higher cost, how by fluorine-containing reagent and reaction
The screening of condition, preparing, there is water-soluble, low cost fluorine-containing polyethyleneimine turn it in seperation film, adsorbent even gene
Contaminating the fields such as material, specifically better application prospect is problem to be solved of the present invention.
Summary of the invention
It is an object of the invention to solve the scarcity of the fluorine-containing cross-linked material of water-soluble low cost, providing one kind can be used for point
The preparation method of novel low-cost functional fluoropolymer material from film preparation, gene transfection Materials and adsorbent material.
The present invention is achieved through the following technical solutions:
A kind of structure fragment general formula of fluorine-containing polyethyleneimine functional material is as follows:
Wherein dotted line represents N atom connection branch or hydrogen, Z be sulfonyl () or acyl group ()；R is perfluoroalkyl,
General formula CnF2n+1, n 1-18.
A kind of preparation method of fluorine-containing polyethyleneimine functional material, includes the following steps, polyethyleneimine is dissolved in
In solvent, perfluoroalkyl carboxylic acid halides or per-fluoroalkyl sulfonyl halogen are added dropwise into the solution, in a heated condition, after being stirred to react
Solvent is removed, the fluorine-containing polyethyleneimine material is obtained.
The preparation method of fluorine-containing polyethyleneimine material according to the present invention, polyethyleneimine are substrate, molecule
Amount is 600 Da, 1800 Da, the one or more of 10000 Da and 70000 Da；
The preparation method of fluorine-containing polyethyleneimine material according to the present invention, related fluorination reagent perfluoroalkyl acyl
Halogen general structure is, per-fluoroalkyl sulfonyl halogen general structure is, wherein R is perfluoroalkyl, general formula
CnF2n+1, n 1-18, X are halogen atom, including fluorine, chlorine, bromine, one of iodine.
The preparation method of fluorine-containing polyethyleneimine material according to the present invention, which is characterized in that involved in step
Fluorination reagent and the mass ratio of polyethyleneimine substrate include range from 1:1 ~ 1:100.
The preparation method of fluorine-containing polyethyleneimine material according to the present invention, reaction dissolvent include methanol, and ethyl alcohol is different
Propyl alcohol, acetonitrile, toluene, pyridine, tetrahydrofuran, n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc),
N-Methyl pyrrolidone (NMP), one or more of dimethyl sulfoxide.
The preparation method of fluorine-containing polyethyleneimine material according to the present invention, heating temperature are 25 DEG C ~ 120
℃。
The utility model has the advantages that
The advantage of the invention is that multi-solvents is selected to guarantee the dissolution of reactant to promote the generation of reaction, and then improve poly- second
The fluorinated graft rate of alkene imines passes through the grafting rate of the adjustable full-fluorine group of the control of reaction condition.Gained fluorinated polyethylene is sub-
The amidine functional group of amine full-fluorine group segment and high reaction activity containing low-surface-energy simultaneously, convenient for applied to crosslinking, surface
The processes such as coating prepare microballoon and film, are a kind of cost-efficiently functionalization cross-linked materials.
Detailed description of the invention
Fluorine-containing polyethyleneimine infared spectrum described in Fig. 1 embodiment 1.
Fluorine-containing polyethyleneimine nuclear magnetic spectrum described in Fig. 2 embodiment 1.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described further, but the embodiment given is not constituted and wanted to right
Ask the limitation of saturation range.
Embodiment 1
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 1800 molecular weight polyethyleneimines, fluorination reagent perfluoro butyl
Sulfuryl fluoride, fluorinated volume are 40 wt%, (1: 2.5)
5 g of polyethyleneimine of 600 Da molecular weight is added into eggplant-shape bottle, 50 mL of DMF is added, being heated to 60 degrees Celsius will
It is dissolved.2 g of perfluoro butyl sulfonic acid fluoride is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.It is removed with Rotary Evaporators
Solvent is removed, then vacuum drying obtains the fluorinated polyethylene imine product of 40 wt% grafting amounts.
Product infared spectrum is as shown in Figure 1, comparison original PEI infared spectrum, N-H stretch shock absorption (3354 cm-1,
3328-1) obviously weaken, CF3、CF2There are (1204 cm in group characteristic absorption-1、1130 cm-1).Product nuclear magnetic spectrum such as Fig. 2 institute
Show, chemical shift -82.3 ppm, -114.4 ppm, -122.2 ppm and -127.1 ppm respectively correspond the CF on perfluoro butyl3
With three groups of CF2Group.Fluorine signal, which broadens, proves that it is grafted on polymer P EI.Impurity is mainly perfluoro butyl sulfonic acid, and content <
5%.Prove product grafting rate > 95%.
Embodiment 2
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 600 molecular weight polyethyleneimines, fluorination reagent perfluor butyryl
Chlorine, fluorinated volume are 100 wt% (1: 1)
5 g of polyethyleneimine of 600 Da molecular weight is added into eggplant-shape bottle, 50 mL toluene are added, being heated to 60 degrees Celsius will
It is dissolved.5 g of perfluor butyl chloride is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.It is removed with Rotary Evaporators molten
Agent, then vacuum drying obtains the fluorinated polyethylene imine product of 100 wt% grafting amounts.
Embodiment 3
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 70000 molecular weight polyethyleneimines, fluorination reagent perfluoro butyl
Sulfuryl fluoride, fluorinated volume are 1 wt%(1: 100)
5 g of polyethyleneimine of 70000 Da molecular weight is added into eggplant-shape bottle, 50 mL DMF and 10 mL isopropanols are added, add
Heat is dissolved to 60 degrees Celsius.50 mg of perfluoro butyl sulfonic acid fluoride is slowly added dropwise at this temperature, magnetic agitation reaction 12 is small
When.Solvent is removed with Rotary Evaporators, then vacuum drying obtains the fluorinated polyethylene imine product of 1 wt% grafting amount.
Embodiment 4
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 600 molecular weight polyethyleneimines, fluorination reagent perfluoro capryl sulphur
Acyl fluorides, fluorinated volume are 20 wt%(1: 5)
The polyethyleneimine 5g of 600 Da molecular weight is added into eggplant-shape bottle, 50 mL acetonitriles and 10 mL isopropanols, heating is added
It is dissolved to 60 degrees Celsius.1 g of perfluoro butyl sulfonic acid fluoride is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.With
Rotary Evaporators remove solvent, and then vacuum drying obtains the fluorinated polyethylene imine product of 20 wt% grafting amounts.
Embodiment 5
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 600 molecular weight polyethyleneimines, fluorination reagent perfluoro capryl sulphur
Acyl fluorides, fluorinated volume are 20 wt%(1: 5)
The polyethyleneimine 5g of 600 Da molecular weight is added into eggplant-shape bottle, 50 mL toluene and 10 mL isopropanols, heating is added
It is dissolved to 60 degrees Celsius.1 g of full-fluorine octyl sulfuryl fluoride is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.With
Rotary Evaporators remove solvent, and then vacuum drying obtains the fluorinated polyethylene imine product of 20 wt% grafting amounts.
Embodiment 6
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 600 molecular weight polyethyleneimines, fluorination reagent perfluoro-octanoyl
Chlorine, fluorinated volume are 20 wt%(1: 5)
5 g of polyethyleneimine of 600 Da molecular weight is added into eggplant-shape bottle, 50 mL NMP and 10 mL isopropanols, heating is added
It is dissolved to 60 degrees Celsius.1 g of perfluorooctane chloride is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.With rotation
Evaporimeter removes solvent, and then vacuum drying obtains the fluorinated polyethylene imine product of 20 wt% grafting amounts.
Embodiment 7
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 600 molecular weight polyethyleneimines, fluorination reagent perfluor butyryl
Fluorine, fluorinated volume 20wt%(1: 5)
Be added the polyethyleneimine 5g of 600 Da molecular weight into eggplant-shape bottle, 50 mL pyridines be added, be heated to 60 degrees Celsius by its
Dissolution.1 g of perfluor butyryl fluorine is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.Solvent is removed with Rotary Evaporators,
Then vacuum drying obtains the fluorinated polyethylene imine product of 20 wt% grafting amounts.
Embodiment 8
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 600 molecular weight polyethyleneimines, fluorination reagent fluoroform sulphur
Acyl chlorides, fluorinated volume are 20 wt%(1: 5)
5 g of polyethyleneimine of 600 Da molecular weight is added into eggplant-shape bottle, 50 mL DMF are added, being heated to 25 degrees Celsius will
It is dissolved.1 g of trifluoromethanesulfonyl chloride is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.It is removed with Rotary Evaporators
Solvent is removed, then vacuum drying obtains the fluorinated polyethylene imine product of 20 wt% grafting amounts.
Embodiment 9
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 600 molecular weight polyethyleneimines, fluorination reagent perfluor palmityl
Chlorine, fluorinated volume are 10 wt%(1: 10)
The polyethyleneimine 5g of 600 Da molecular weight is added into eggplant-shape bottle, DMAc is added, is heated to 60 degrees Celsius and is dissolved.
1 g of perfluor hexadecanoyl chloride is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.Solvent is removed with Rotary Evaporators, so
Vacuum drying obtains the fluorinated polyethylene imine product of 10 wt% grafting amounts afterwards.
Embodiment 10
The synthesis of fluorine-containing polyethyleneimine functional material, substrate are 70000 molecular weight polyethyleneimines, fluorination reagent perfluoro butyl
Sulfuryl fluoride, fluorinated volume are 5 wt%(1: 20)
5 g of polyethyleneimine of 70000 Da molecular weight is added into eggplant-shape bottle, 50 mL DMF are added, are heated to 120 degrees Celsius
It is dissolved.250 mg of perfluoro butyl sulfonic acid fluoride is slowly added dropwise at this temperature, magnetic agitation is reacted 12 hours.Use rotary evaporation
Instrument removes solvent, and then vacuum drying obtains the fluorinated polyethylene imine product of 5 wt% grafting amounts.
Claims (7)
1. a kind of fluorine-containing polyethyleneimine functional material, the structure fragment general formula of the fluorinated material are as follows:
Wherein dotted line represents N atom connection branch or hydrogen, and Z is sulfonyl or acyl group；R is perfluoroalkyl, general formula CnF2n+1, n 1-
18。
2. a kind of synthetic method of fluorine-containing polyethyleneimine functional material, which is characterized in that include the following steps, by polyethyleneimine
Amine is dissolved in solvent, and perfluoroalkyl carboxylic acid halides or per-fluoroalkyl sulfonyl halogen are added dropwise into the solution, and in a heated condition, stirring is anti-
Solvent is removed after answering, and obtains fluorine-containing polyethyleneimine material.
3. the synthetic method of the fluorine-containing polyethyleneimine functional material as described in claim 2, which is characterized in that polyethylene
Its molecular weight of imines is 600 Da, 1800 Da, the one or more of 10000 Da and 70000 Da.
4. the synthetic method of the fluorine-containing polyethyleneimine functional material as described in claim 2, which is characterized in that related
Fluorination reagent is perfluoroalkyl carboxylic acid halides or per-fluoroalkyl sulfonyl halogen.
5. the synthetic method of the fluorine-containing polyethyleneimine functional material as described in claim 2, which is characterized in that in step
The mass ratio of related fluorination reagent and polyethyleneimine is 1:1 ~ 1:100.
6. the synthetic method of the fluorine-containing polyethyleneimine functional material as described in claim 2, which is characterized in that reaction dissolvent
For methanol, ethyl alcohol, isopropanol, acetonitrile, toluene, pyridine, tetrahydrofuran, n,N-Dimethylformamide, N, N- dimethylacetamide
Amine, N-Methyl pyrrolidone, one or more of dimethyl sulfoxide.
7. the synthetic method of the fluorine-containing polyethyleneimine functional material as described in claim 2, which is characterized in that heating temperature
It is 25 DEG C ~ 120 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114848830A (en) * | 2022-04-26 | 2022-08-05 | 复旦大学附属眼耳鼻喉科医院 | Preparation for improving corneal crosslinking effect and corneal crosslinking combined preparation |
| CN116731557A (en) * | 2023-07-26 | 2023-09-12 | 江苏唐彩新材料科技股份有限公司 | High-water-resistance polyamide printing ink and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114848830A (en) * | 2022-04-26 | 2022-08-05 | 复旦大学附属眼耳鼻喉科医院 | Preparation for improving corneal crosslinking effect and corneal crosslinking combined preparation |
| CN116731557A (en) * | 2023-07-26 | 2023-09-12 | 江苏唐彩新材料科技股份有限公司 | High-water-resistance polyamide printing ink and preparation method thereof |
| CN116731557B (en) * | 2023-07-26 | 2024-03-05 | 江苏唐彩新材料科技股份有限公司 | High-water-resistance polyamide printing ink and preparation method thereof |
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